EP0894116A1 - Matieres de moulage polyamide rendues stables a l'oxydation - Google Patents

Matieres de moulage polyamide rendues stables a l'oxydation

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Publication number
EP0894116A1
EP0894116A1 EP97918139A EP97918139A EP0894116A1 EP 0894116 A1 EP0894116 A1 EP 0894116A1 EP 97918139 A EP97918139 A EP 97918139A EP 97918139 A EP97918139 A EP 97918139A EP 0894116 A1 EP0894116 A1 EP 0894116A1
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EP
European Patent Office
Prior art keywords
copper
alkyl
weight
molding compositions
thermoplastic molding
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EP97918139A
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German (de)
English (en)
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EP0894116B1 (fr
Inventor
Stefan Grutke
Peter Comba
Charis Katsichtis
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only

Definitions

  • the present invention relates to thermoplastic molding compositions containing
  • the invention relates to the use of the molding compositions for the production of moldings of all kinds and the moldings obtainable here.
  • EP-A 463 512 describes stabilizer combinations of copper (I) halides, triphenylphosphine and amines for impact-modified polyamides.
  • the addition of aminic antioxidants often causes direct discoloration as well as discoloration under thermal stress.
  • thermoplastic molding compositions which show improved heat stabilization and are less prone to discoloration. We have found that this object is achieved by the thermoplastic molding compositions defined above.
  • the copper compounds added for stabilization can be obtained by reacting copper (I) salts with known and new phosphate chelate ligands.
  • the invention further relates to phosphorus sulfo compounds of the formula II which can be used as chelate ligands.
  • Suitable copper (I) salts are both copper salts of organic acids, for example acetic acid, and of inorganic acids, such as hydrocyanic acid or thiocyanic acid, preferably hydrohalic acids. From the group of copper halides copper fluoride, copper chloride, copper bromide, copper iodide, the latter three are given preference, where copper iodide is particularly suitable.
  • R 1 and R 2 independently of one another Ci-Cg-alkyl, C 5 -Cs-cycloalkyl or phenyl, which may be 1 to 5 times with
  • R 3 and R 4 independently of one another Ci-Cs-alkyl, C 5 -Cs-cycloalkyl,
  • Phenyl which is optionally substituted with -CC 4 alkyl, -B 1 -PR 2 R 2 , B 2 -SR 5 , B 2 -OR 5 and R 3 and R 4 together
  • B 2 , B 3 , B 4 independently of one another for Ci-Ce -alkylene, naphthylene, Phenylene, benzylene and
  • R 5 represents C 1 -C 4 -alkyl or hydrogen
  • the substituents B 3 -, B 2 , B 3 and B 4 are, independently of one another, methylene, ethylene, n-propylene, isopropylene, n-butylene, n-pentylene, n-hexylene, 1,1'- or 2,2 '-Naphthylene, 1,4-phenylene and para-benzylene suitable.
  • Suitable substituents R 1 , R 2 , R 3 , R 4 and R 5 are, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • R 1 , R 2 , R 3 and R 4 are also, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, cyclopentyl, cyclohexyl, cyclo - heptyl, cyclooctyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-isopropylphenyl, 2, 4, 6-trimethylphenyl, 2, 4 -dimethylphenyl and 4-tert. -Butylphenyl.
  • n the number 1, 2 or 3, are obtained.
  • phosphate chelate ligands in which B 1 is a methylene, ethylene, propylene, butylene or naphthylene bridge.
  • Unbranched alkyl radicals are preferred for R 1 , R 2 , R 3 and / or R 4 .
  • Unsubstituted phenyl radicals are also preferred.
  • Phosphine chelate ligands in which R 1 and R 2 are cyclohexyl or phenyl are particularly preferred.
  • Suitable phosphine chelate ligands are, for example, 1,2-bis (dim-methylphosphmo) ethane, bis (2-diphenylphosphinoethyl) phenylphosphm, 1,6- (bis (diphenylphosphino) hexane and 1,5-bis ( diphenylphosphino) pentane.
  • Particularly preferred phosphate chelate ligands are, for example, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 2,2'-bis (diphenylphosphino) -1,1 '-bmaphthyl, 1,3-bis (dicyclohexylphosphmo) propane and 1,4-bis (diphenylphosphino) butane.
  • the phosphate chelate ligands can be prepared according to the reactions generally known for organophosphorus compounds, as described in Advanced Organic Chemistry: reactions, mechamsms and structure, J. March, Wiley-Interscience Publication, 4, 1992, p. 413 and Inorg. Chemistry of the Transition Elements - Vol. 6, The Chemical Society, 1978, Johnson, Gilbert, p. 272 ff, Methods of organic chemistry, Houben-Weyl, XII / 1, Georg Thieme Verlag, Stuttgart, 1963, p. 17 -66 described.
  • phosphorus halides with Grignard compounds or by reacting phosphors with alkyl halides under reducing conditions, e.g. Sodium amide in liquid ammonia or sodium in liquid ammonia.
  • phosphate chelate ligands are commercially available.
  • the present application also relates to new phosphorus sulfo compounds of the general formula (III)
  • B 1 and B 2 independently of one another Ci-C e alkylene, naphthylene, phenylene, benzylene,
  • R 1 and R 2 independently of one another Ci-Cs-alkyl, C5-C8-cycloalkyl or phenyl, which is optionally substituted with Ci C 4 -alkyl, and
  • R 5 C ⁇ -C 4 alkyl or hydrogen
  • the new phosphine chelate ligands III are also prepared by known reactions.
  • a first reaction step for example, 2 moles of a monoalkylphosphate are reacted with one mole of dibromoalkane under reducing conditions such as sodium in liquid ammonia to give bisphosphine IV, in accordance with the following general reaction equation
  • the further synthesis takes place by reaction of IV with a monothia cycle and further reducing conditions with ring opening.
  • the dithiol thus obtained can optionally be converted into its thioether after known reactions.
  • chelating ligands is only intended to express that the phosphine compounds have several coordination points for possible complex formation.
  • the phosphine chelate ligands are reacted with the copper (I) salt in a molar ratio of 1: 1 to a ratio of 5: 1.
  • the one to three times molar amount of phosphine chelating ligand is preferably chosen. It is assumed that the copper (I) salts form coordinative compounds with the phosphine chelate ligands, so that when there are several coordination sites, mixtures of differently coordinated copper compounds can naturally also occur. Depending on the selected ratio of phosphine chelate ligand to copper (I) salt, unreacted ligand may also be present in the mixture, but this is not disadvantageous.
  • the copper (I) halides are reacted with the phosphine chelate ligands in an inert solvent / diluent or in the melt without solvent.
  • Inert solvents / diluents are, for example, ketones such as acetone and cyclohexane, cyclic ethers such as tetrahydrofuran and dioxane, dialkyl ethers such as diethyl ether, halogenated hydrocarbons such as methylene chloride, dichloroethane, carbon tetrachloride and chloroform. Acetone, tetrahydrofuran and chloroform are preferred as solvents. The reaction in the melt is preferred since the solvent does not subsequently have to be removed.
  • the copper (I) salt is metered into the molten or dissolved phosphate chelate ligand.
  • reaction in an inert gas atmosphere such as nitrogen is expedient, if not necessary, since the oxidation stability of the copper compounds decreases slightly at higher temperatures, such as the melt.
  • the molding compositions preferably contain the copper compound in an amount of from 10 to 1000 ppm, particularly preferably from 50 to 35 500 ppm of copper, based on polyamide. Higher amounts of copper compound, e.g. 2% by weight, preferably 1% by weight in concentrates are possible.
  • the molding compositions according to the invention contain 30 to 100, preferably 40, 40 to 90 and in particular 60 to 80% by weight of a mixture of polyamide and a stabilizing amount of a copper compound obtainable by reacting copper (I) salts with phosphate chelate ligands (component A) .
  • the polyamides of the molding compositions according to the invention generally have a relative viscosity ⁇ re ⁇ of 1.7 to 5.0, determined in a 1% by weight solution containing 96% by weight sulfuric acid 25 ° C. Polyamides with a relative viscosity of 1.7 to 4.5, in particular 2.5 to 4.0, are preferably used.
  • polyamides derived from lactams with 7 to 13 ring members such as polycaprolactam, polycapryllactam and polylactic lactam, and polyamides obtained by reacting dicarboxylic acids with diams.
  • Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids.
  • Examples include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid as acids.
  • Particularly suitable diams are alkane diams with 6 to 12 ms, particularly 6 to 8 carbon atoms, and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-ammocyclohexyl) methane, 2,2-di (4-) ammophenyl) propane or 2,2-D ⁇ - (4-ammocyclohexyl) propane.
  • Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam.
  • Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-dimobutane with adipic acid at elevated temperature (polyamide 4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • polyamides which are obtainable by copolymerization of two or more of the aforementioned monomers, or
  • Mixtures of several polyamides are suitable, the mixture ratio is arbitrary.
  • Such partially aromatic, partially stable copolyamides are composed, for example, of: Ai) 20-90% by weight of units derived from terephthalic acid and hexamethylene diamine,
  • a 3 0-80% by weight of units which are derived from adipic acid and hexamethylene diamm,
  • the proportion of component (A 2 ) and / or (A 3 ) and / or (A 4 ) being at least 10% by weight.
  • Component Ai) contains 20-90% by weight of units which are derived from terephthalic acid and hexamethylene diamine.
  • the copolyamides contain units which are derived from ⁇ -caprolactam and / or units which are derived from adipic acid and hexamethylene diamine and / or units which are derived from further polyamide-forming monomers.
  • the proportion of units derived from ⁇ -caprolactam is a maximum of 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from Derive adipic acid and hexamethylene diamine, amounts to up to 80% by weight, preferably 30 to 75% by weight and in particular 35 to 60% by weight.
  • the copolyamides can also contain units of ⁇ -caprolactam as well as units of adipic acid and hexamethylene diamine; In this case it is advantageous if the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight.
  • the ratio of the units derived from ⁇ -caprolactam and from adipic acid and hexamethylene diamine is not subject to any particular restriction.
  • Polyamides with 50 to 80, in particular 60 to 75,% by weight units derived from terephthalic acid and hexamethylene diamine (units Ai) and 20 to 50, preferably 25 to 40,% by weight of Ein ⁇ have been found to be particularly advantageous for many applications units which are derived from ⁇ -caprolactam (units A 2 )).
  • the partially aromatic copolyamides can contain amounts of up to 40, preferably 10-30% by weight and in particular 20-30% by weight of further poly amide-forming monomers A 4 ); as they are known from other polyamides.
  • Aromatic dicarboxylic acids A 4 have 8 to 16 carbon atoms.
  • Suitable aromatic dicarboxylic acids are, for example, isophthalic acid, substituted terephthalic and isophthalic acids such as 3-t-butyl-isophthalic acid, polynuclear dicarboxylic acids, eg. B.
  • Further polyamide-forming monomers A 4 can be derived from dicarboxylic acids with 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines with 4 to 16 carbon atoms and from aminocarboxylic acids or corresponding lactams with 7 to 12 carbon atoms.
  • Suitable monomers of these types include subennic acid, azelaic acid or sebacic acid as representatives of the aliphatic dicarboxylic acids, 1, 4-butanediamine, 1, 5-pentanediamine, piperazine as representatives of the diam and caprylic lactam, anthnanthlactam, ⁇ -ammoundecanoic acid and laurel lactam as representatives of lactams or aminocarboxylic acids.
  • compositions of component (A) are particularly preferred:
  • component (A 4 ) contains cyclic aliphatic diams as polyamide building systems, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyDmethane, bis (4-aminocyclohexyl) - 2, 2 propane, bis (4 -ammo-3 -methylcyclohexyl) -2, 2-propane, cyclohexanediamine and isophoronediamine are preferred, such partially aromatic, partially crystalline polyamides are described in DE A 44 04 250.
  • those partially aromatic copolyamides have proven to be particularly advantageous whose triamm content is less than 0.5, preferably less than 0.3% by weight.
  • These copolyamides can be prepared by the processes described in EP-A 129 195 and 129 196.
  • thermoplastic molding compositions according to the invention can contain 0 to 70, preferably up to 35, in particular 15 to 35,% by weight of further additives.
  • further additives are primarily fibrous or particulate fillers (component B) or rubber-elastic polymers (component C) and mixtures thereof.
  • Preferred fibrous reinforcing materials are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the thermoplastic polyamide. In general, the glass fibers used have a diameter in the range from 6 to 20 ⁇ m, preferably from 10 to 14 ⁇ m.
  • the average length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.
  • Amorphous silica, magnesium carbonate (chalk), kaolin (in particular calcined kaolin), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite are suitable as particulate fillers.
  • Preferred combinations of fillers are, for example, 20% by weight of glass fibers with 15% by weight of wollastonite and 15% by weight of glass fibers with 15% by weight of wollastonite.
  • the molding compositions can contain 0 to 30, preferably up to 20 and, in particular, 10 to 15% by weight of a rubber-elastic polymer C (often also referred to as impact modifier or rubber).
  • a rubber-elastic polymer C (often also referred to as impact modifier or rubber).
  • Preferred rubber-elastic polymers are polymers based on olefins, which are composed of the following components:
  • Ci 40 to 100 wt .-% of at least one ⁇ -olefin with 2 to 8 carbon atoms
  • component (C) is not an olefin homopolymer
  • the first preferred group is the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers, which preferably have a ratio of ethylene to propylene units in the range from 40:60 to 90:10 exhibit.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • the Mooney viscosities (MLI + 4/100 ° C.) of such, preferably non-crosslinked, EPM or EPDM rubbers are preferably in the range from 25 to 100 ms - especially from 35 to 90 (measured on the large rotor after 4 minutes running time at 100 ° C according to DIN 53 523).
  • EPM rubbers generally have no more double fertilizers, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms
  • diene monomers C 2 are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa- 1, 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5 -Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15% by weight, based on the total weight of the olefin polymer.
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
  • Acrylic acid, methacrylic acid and their derivatives and maleic anhydride are particularly mentioned here.
  • Another group of preferred olefin polymers are copolymers of ⁇ -olefins having 2-8 C atoms, in particular of ethylene, with Ci-Cig alkyl esters of acrylic acid and / or methacrylic acid.
  • C ⁇ _ C 8 alkyl ester of acrylic acid or methacrylic acid but are esters having 1-12 C atoms, in particular having 2-10 C atoms Trust ⁇ Trains t.
  • Examples include methyl, ethyl, propyl, n-, i-butyl and 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the proportion of methacrylic acid esters and acrylic acid esters C 3 ) in the olefin polymers is 0-60, preferably 10-50 and in particular 30-45% by weight.
  • the olefin polymers may also contain acid-functional and / or latently acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids C 4 ) or monomers C 5 ) having epoxy groups.
  • monomers C 4 ) are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert. -Butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters.
  • Latent acid-functional monomers are to be understood as those compounds which, under the polymerization conditions or when the olefin polymers are incorporated, form the molding compositions free acid groups.
  • Examples of these are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C 1 -C 2 -alkyl esters of the abovementioned acids, in particular tert. -Butyl acrylate and tert-butyl methacrylate listed.
  • the acid-functional or latent acid-functional monomers and the epoxy group-containing monomers are preferably incorporated by adding compounds of the general formulas IV-VII to the monomer mixture m the olefin polymers
  • radicals R 1 - R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20 and n is an integer from 0 to 10.
  • Hydrogen is preferred for R 1 -R 7 , 0 or 1 for m and 1 for n.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, C 4 ) or alkenyl glycidyl ether or methyl glycidyl ether C 5 ).
  • Preferred compounds of the formulas IV, V, VI and VII are maleic acid and maleic anhydride as component C 4 ) and epoxy group-containing esters of acrylic acid and / or methacrylic acid, glycidyl acrylate and glycidyl methacrylate (as component C 5 ) being particularly preferred.
  • the proportion of components C 4 ) and C 5 ) is 0.07 to 40% by weight, in particular 0.1 to 20 and particularly preferably 0.15 to 15% by weight, based on the total weight of the olefin polymers .
  • Olefin polymers of are particularly preferred
  • n-butyl acrylate and / or 2-ethylhexyl acrylate 1 to 45, in particular 10 to 35% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and ⁇ -butyl esters.
  • the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.
  • the melt index of the ethylene copolymers is generally in the range from 1 to 80 g / 10 mm (measured at 190 ° C. and 2.16 kg load)
  • suitable elastomers (C) are, for example, emulsion polymers, the preparation of which, e.g. in Houben-Weyl, Methods of Organic Chemistry, Volume XII. I (1961) and Blackley m in the monograph "Emulsion Polymerization".
  • Monomers for the production of the elastomers are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, and mixtures thereof. These monomers can be combined with other monomers such as styrene, acrylonitrile, methyl ethers and further acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and prcpylacrylate can be copolymerized.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • the emulsion polymers can be completely or partially crosslinked.
  • Monomers acting as crosslinkers are, for example, buta-1,3-diene, divmylbenzene, diallyl phthalate and dihydro dicyclopentadienyl acrylate and the compounds described in EP-A 50 265.
  • Graft-crosslinking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds which react at different speeds in the polymerization.
  • graft-crosslinking monomers examples include monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl groups in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • suitable graft-crosslinking monomers for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • the proportion of these crosslinking monomers in component (C) is up to 5% by weight, preferably not more than 3% by weight, based on (C).
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers and graft polymers with an inner core made of n-butyl acrylate and an outer shell made of copolymers mentioned above.
  • the elastomers (C) described can also be prepared by other customary methods, for example by suspension polymerization.
  • Other common additives are, for example, stabilizers and oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and pigments, plasticizers and processing aids.
  • Their proportion is generally up to 30, preferably up to 15,% by weight, based on the total weight of the molding compositions.
  • Pigments and dyes are generally contained in amounts of up to 4, preferably 0.5 to 3.5 and in particular 0.5 to 3% by weight.
  • the pigments for the coloring of thermoplastics are generally known, see, for example, R. Gachter and H. Muller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510.
  • the first preferred group of pigments are white pigments such as Zmkoxid, Zmksulfid , Lead white (2 PbC0 3 Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • the rutile form is used in particular for the white coloring of the molding compositions according to the invention.
  • Black color pigments which can be used according to the invention are iron oxide black (Fe 3 0 4 ), spinel black (Cu (Cr, Fe) 2 0 4 ), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black and particularly preferably carbon black , which is usually used in the form of furnace or gas black (see G. Benzmg, Pigments for Paints, Expert-Verlag (1988), p. 78ff).
  • inorganic colored pigments such as chrome oxide green or organic can be used to adjust certain hues
  • Colored pigments such as azo pigments and phthalocyanines can be used according to the invention. Pigments of this type are generally commercially available.
  • pigments or dyes mentioned in a mixture e.g. Carbon black with copper phthalocyanines, since it is generally easier to disperse colors in thermoplastics.
  • UV stabilizers are various substituted resorbents, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight.
  • Lubricants and mold release agents which are generally added in quantities of up to 1% by weight of the thermoplastic composition, are stearic acid, stearyl alcohol, alkyl stearate esters and amides, and also esters of pentaerythritol with long-chain fatty acids. It salts of calcium, zinc or aluminum of stearic acid and dialkyl ketones, for example distearyl ketone, can also be used.
  • the additives are stabilizers which the cerium ⁇ reduction of the red phosphorus in the presence of moisture and atmospheric oxygen prevent.
  • Compounds of cadmium, zinc, aluminum, tin, magnesium, manganese and titanium may be mentioned as examples.
  • Particularly suitable compounds are, for example, oxides of the metals mentioned, furthermore carbonates or oxicarbonates,
  • Hydroxides and salts of organic or inorganic acids such as acetates or phosphates or hydrogen phosphates.
  • thermoplastic molding compositions according to the invention can be produced by processes known per se by mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruding them. After the extrusion, the extrudate is cooled and comminuted.
  • the stabilizing copper connection can be made directly via a
  • the degassing extruder usually has suitable mixing elements, such as kneading blocks , Is provided.
  • the extrudate is then also extruded, cooled and granulated.
  • the molding compositions according to the invention are notable for greater heat resistance.
  • they can be processed thermoplastically without any problems and are accordingly suitable for the production of fibers, foils and moldings. They also show significantly better color results.
  • a further increase in heat stabilization can be achieved by adding alkali halides.
  • the potassium salts are preferred from the group of lithium, sodium and potassium halides.
  • suitable halides are fluorides, chlorides, and preferably bromides and iodides. Of particular note is the increase in the stabilizing effect of potassium bromide and potassium iodide.
  • the inorganic alkali halides of the molding composition are used in an amount of 1 to 3,000 ppm, preferably 10 to
  • thermoplastic molding compositions (Examples 1 to 9)
  • Copper based on polyamide as a stabilizer, optionally with the glass fiber and optionally potassium iodide (750 ppm potassium iodide based on polyamide).
  • composition of the molding compounds and the comparative molding compounds can be found in Table 1.
  • thermoplastic molding compositions of Examples 1 to 13 Application properties of the thermoplastic molding compositions of Examples 1 to 13
  • a measure of the stabilizing effect of additives is the decrease in the impact strength values and the tensile modulus of elasticity after storage at elevated temperature. For this purpose, both values were determined before and after 240 or 600 h storage at 150 ° C. in a circulating drying oven.
  • reaction mixture was fractionally distilled in vacuo. 115 g of cyclohexylphosphonyl dichloride (boiling point 141 ° C. at 1.2 Torr) were obtained as 01, which installed m white needles.

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Abstract

L'invention concerne des matières de moulage thermoplastiques contenant entre 30 et 100 % en poids d'un mélange de polyamide et d'une quantité à action stabilisante d'un composé cuivreux obtenu par réaction de sels cuivreux avec des ligands de chélate de phosphine, et entre 0 et 70 % en poids d'autres additifs.
EP97918139A 1996-04-19 1997-04-17 Matieres de moulage polyamide rendues stables a l'oxydation Expired - Lifetime EP0894116B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19615484 1996-04-19
DE19615484A DE19615484A1 (de) 1996-04-19 1996-04-19 Oxidationsstabilisierte Polyamidformmassen
PCT/EP1997/001910 WO1997040100A1 (fr) 1996-04-19 1997-04-17 Matieres de moulage polyamide rendues stables a l'oxydation

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EP0894116A1 true EP0894116A1 (fr) 1999-02-03
EP0894116B1 EP0894116B1 (fr) 1999-12-15

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US (1) US6011099A (fr)
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DE19925221B4 (de) * 1998-06-02 2017-05-18 Asahi Kasei Kabushiki Kaisha Schwarz gefärbte verstärkte Polyamidharz-Zusammensetzung
DE19847627A1 (de) * 1998-10-15 2000-04-20 Brueggemann L Kg Mit Kupferkomplexen und organischen Halogenverbindungen stabilisierte Polyamidzusammensetzung
KR20070046797A (ko) * 2004-07-01 2007-05-03 솔베이 어드밴스트 폴리머스 엘.엘.씨. 방향족 폴리아미드 조성물 및 이로부터 제조된 제품

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US3294870A (en) * 1964-03-24 1966-12-27 American Cyanamid Co Organophosphorus-copper complex compounds and their use for producing fire retardant plastics
DE1237309B (de) * 1965-09-11 1967-03-23 Bayer Ag Verfahren zur Herstellung waermestabilisierter Polyamide
DE4020447A1 (de) * 1990-06-27 1992-01-02 Bayer Ag Stabilisatorkombinationen und ihre verwendung zur herstellung von stabilisierten, schlagzaehmodifizierten polyamiden
US5550305A (en) * 1991-10-16 1996-08-27 Amoco Corporation Ethylene trimerization
DE4444378A1 (de) * 1994-12-14 1996-06-20 Basf Ag Thermoplastische Formmassen auf der Basis von teilaromatischen Polyamiden und Polymethacrylimiden

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See references of WO9740100A1 *

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DE59700853D1 (de) 2000-01-20
DE19615484A1 (de) 1997-10-23
US6011099A (en) 2000-01-04
WO1997040100A1 (fr) 1997-10-30
EP0894116B1 (fr) 1999-12-15

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